Method for the preparation of an alkoxy-functional organohydrogensiloxane oligomer and use of said oligomer

ABSTRACT

A method for the preparation of an alkoxy-functional hydrogensiloxane oligomer includes reacting a polyorganohydrogensiloxane oligomer and an aliphatically unsaturated alkoxysilane in the presence of a hydrosilylation reaction and a promoter. The resulting crude reaction product is treated with a treating agent, and thereafter distilled to produce the alkoxy-functional organohydrogensiloxane oligomer. The alkoxy-functional hydrogensiloxane oligomer can be reacted with polyorganosiloxane having an aliphatically unsaturated monovalent hydrocarbon group to form a polyalkoxy-functional polyorganosiloxane. The polyalkoxy-functional polyorganosiloxane can be formulated in condensation reaction curable compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 62/898,564 filed on 11 Sep. 2019 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Ser. No. 62/898,564 ishereby incorporated by reference.

TECHNICAL FIELD

A method for the preparation of an alkoxy-functional hydrogensiloxaneoligomer is disclosed. The alkoxy-functional hydrogensiloxane oligomercan be reacted with polyorganosiloxane having an aliphaticallyunsaturated monovalent hydrocarbon group to form a polyalkoxy-functionalpolyorganosiloxane, which is useful in condensation reaction curablecompositions.

BACKGROUND

Bis(trimethoxysilylethyl)dimethylsiloxy-n-propylsilane was prepared byhydrosilylation of tris(dimethylsiloxy)-n-propylsilane andvinyltrimethoxysilane catalyzed by platinum, which led tobis(trimethoxysilylethyl)dimethylsiloxy-n-propylsilane in a yield of40%, with the 1:1 and 1:3 adducts as the major byproducts. Thebeta-isomer: alpha-isomer (β:α) ratio was 70:30.

Dimethylacetoxysilane has been proposed as a hydrosilylation reactionpromoter to improve both the yield ofbis(trimethoxysilylethyl)dimethylsiloxy-n-propylsilane from 40% to 75%,and the regioselectivity for beta-isomer from 70% to 88%.

However, this method suffered from the drawback that acetoxy groups werebonded to silicon atoms in the final product when preparing thepolymethoxy-functional polydimethylsiloxane. The acetoxy groups cancause viscosity of the polymethoxy-functional polydimethylsiloxane toincrease with time upon storage as acetic acid was released to catalyzethe condensation reaction.

Problem to be Solved

There is an industry need to provide an acetoxy-free alkoxy-functionalhydrogensiloxane oligomer with high yield and high selectivity to thebeta-isomer.

BRIEF SUMMARY OF THE INVENTION

A method for preparing a product comprising an alkoxy-functionalorganohydrogensiloxane oligomer, where the method comprises:

1) reacting starting materials comprising:

-   -   (A) a polyorganohydrogensiloxane oligomer of unit formula (I):        (HR¹ ₂SiO_(1/2))_(e)(R¹ ₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹        ₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(j)(SiO_(4/2))_(k)        where subscripts e, f, g, h, i, j, and k have values such that        5≥e≥0, 5≥f≥0, 10≥g≥0, 5 h≥0, subscript i is 0 or 1, 5≥j≥0,        subscript k is 0 or 1, with the proviso that a quantity        (e+g+j)≥2, and a quantity (e+f+g+h+i+j+k) 50; and each R¹ is        independently selected from the group consisting of a monovalent        hydrocarbon group of 1 to 18 carbon and a monovalent halogenated        hydrocarbon group of 1 to 18 carbon atoms; and    -   (B) an aliphatically unsaturated alkoxysilane of formula (II):

-   -    where R¹ is as described above, R² is an aliphatically        unsaturated monovalent hydrocarbon group of 2 to 18 carbon        atoms, each R³ is an independently a monovalent hydrocarbon        group of 1 to 18 carbon atoms, and subscript c is 0 or 1; in the        presence of    -   (C) a platinum group metal catalyst; and    -   (D) a hydro(acyloxy)-functional silicon compound of formula        (III):

-   -    where each R⁵ is independently a monovalent hydrocarbon group        of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon        group of 1 to 18 carbon atoms, and R⁶ is a monovalent        hydrocarbon group of 1 to 18 carbon atoms, thereby preparing a        reaction product comprising the alkoxy-functional        organohydrogensiloxane oligomer; and

2) treating the reaction product prepared in step 1) with a treatingagent comprising

-   -   (E) a sorbent selected from the group consisting of        -   (E-1) an activated carbon,        -   (E-2) an ion exchange resin,        -   (E-3) a compound of formula NR⁸ _(x)R⁹ _(y)R¹⁰ _((3-x-y)),            where R⁸, R⁹, and R¹⁰ are each independently selected from            the group consisting of a hydrogen atom and a monovalent            hydrocarbon group of 1 to 18 carbon atoms, subscript x is 0            to 3, subscript y is 0 to 3, and a quantity (x+y)≤3;        -   (E-4) a compound of formula

-   -   -    where R¹¹ is selected from the group consisting of a            hydrogen atom and a monovalent hydrocarbon group of 1 to 18            carbon atoms, and R¹² is a divalent hydrocarbon group of 1            to 18 carbon atoms; and        -   (E-5) a combination of two or more of (E-1) to (E-4); and

    -   (F) a compound of formula HORS, where R⁷ is a hydrogen atom or a        monovalent hydrocarbon group of 1 to 18 carbon atoms, thereby        preparing the product comprising the alkoxy-functional        organohydrogensiloxane oligomer; and

3) distilling the product of step 2), thereby recovering thealkoxy-functional organohydrogensiloxane oligomer.

The alkoxy-functional organohydrogensiloxane oligomer has unit formula(V):

whereR¹, R³, and subscripts c, f, h, i, and k are as described above,subscript b is 0 to 2, m>0, and a quantity (m+n+o+p)=(e+g+j), and each Dis independently a divalent hydrocarbon group of 2 to 18 carbon atoms.

The alkoxy-functional organohydrogensiloxane oligomer is useful in amethod for preparing a polyalkoxy-functional polyorganosiloxane. Themethod for preparing the polyalkoxy-functional polyorganosiloxanecomprises:

(1) reacting starting materials comprising:

(a) the alkoxy-functional organohydrogensiloxane oligomer prepared bythe method described above,

(b) a polyorganosiloxane having, per molecule, an average of at leastone aliphatically unsaturated monovalent hydrocarbon group; and

(c) a hydrosilylation reaction catalyst.

The polyalkoxy-functional polyorganosiloxane is useful in a method forpreparing a condensation reaction curable composition. The method forpreparing the condensation reaction curable composition comprises mixingstarting materials comprising:

(i) the polyalkoxy-functional polyorganosiloxane prepared by the methoddescribed above, and

(ii) a condensation reaction catalyst.

DETAILED DESCRIPTION OF THE INVENTION

In the method described above for preparing the product comprising thealkoxy-functional organohydrogensiloxane oligomer, the followingstarting materials are used. Starting material (A) is apolyorganohydrogensiloxane oligomer, starting material (B) is analiphatically unsaturated alkoxysilane, starting material (C) is ahydrosilylation reaction catalyst, starting material (D) is ahydro(acyloxy)-functional silicon compound, starting material (E) is asorbent, and starting material (F) is a compound of formula HOR⁷, whereR⁷ is a hydrogen atom or a monovalent hydrocarbon group.

(A) Polyorganohydrogensiloxane Oligomer

Ingredient (A) useful in the method described above is apolyorganohydrogensiloxane oligomer of unit formula (I):

(HR¹ ₂SiO_(1/2))_(e)(R¹ ₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(j)(SiO_(4/2))_(k) wheresubscripts e, f, g, h, i, j, and k have values such that 5≥e≥0, 5≥f≥0,10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or 1, withthe proviso that a quantity (e+g+j) 2, and a quantity (e+f+g+h+i+j+k)50; and each R¹ is independently a monovalent hydrocarbon group of 1 to18 carbon or a monovalent halogenated hydrocarbon group of 1 to 18carbon atoms. Alternatively, monovalent hydrocarbon groups for R¹ have 1to 12 carbon atoms, and alternatively 1 to 10 carbon atoms.

Suitable monovalent hydrocarbon groups for R¹ include, but are notlimited to, an alkyl group of 1 to 6 carbon atoms and an aryl group of 6to 10 carbon atoms. Suitable alkyl groups for R¹ are exemplified by, butnot limited to, methyl, ethyl, propyl (e.g., iso-propyl and/orn-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/orsec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl),hexyl, as well as branched saturated hydrocarbon groups of 6 carbonatoms. Suitable aryl groups for R¹ are exemplified by, but not limitedto, phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethyl phenyl.Suitable monovalent halogenated hydrocarbon groups for R¹ include, butare not limited to, a halogenated alkyl group of 1 to 6 carbon atoms, ora halogenated aryl group of 6 to 10 carbon atoms. Suitable halogenatedalkyl groups for R¹ are exemplified by, but not limited to, the alkylgroups described above where one or more hydrogen atoms is replaced witha halogen atom, such as F or Cl. For example, fluoromethyl,2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl,4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl,6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl,2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl,and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl,2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl are examples ofsuitable halogenated alkyl groups. Suitable halogenated aryl groups forR¹ are exemplified by, but not limited to, the aryl groups describedabove where one or more hydrogen atoms is replaced with a halogen atom,such as F or Cl. For example, chlorobenzyl and fluorobenzyl are suitablehalogenated aryl groups. Alternatively, each R¹ is independently methyl,ethyl or propyl. Each instance of R¹ may be the same or different.Alternatively, each R¹ is a methyl group. Examples of suitablehydridosilanes include trimethylsilane and trimethoxysilane.

Step 1) of the method described above produces a reaction productcomprising the alkoxy-functional organohydrogensiloxane oligomer. Thealkoxy-functional organohydrogensiloxane oligomer has unit formula (V):

whereR¹, R³, and subscripts c, f, h, i, and k are as described above,subscript b is 0 to 2, subscript m>0, and subscripts m, n, o, and p havevalues such that a quantity (m+n+o+p)=(e+g+j), and each D isindependently a divalent hydrocarbon group of 2 to 18 carbon atoms.Subscripts e, g, and j are as described above in formula (I). The methoddescribed herein provides the benefit that this alkoxy-functionalorganohydrogensiloxane oligomer is produced with high selectivity to theβ-adduct compounds, i.e., where each D is linear, with either none orlower amounts of the corresponding a-adduct compounds (having one ormore instances of D being non-linear) than existing methods that do notinclude a promoter.

In an alternative embodiment, ingredient (A) is an α,γ-hydrogenterminated organohydrogensiloxane oligomer of formula (VI):

where each R¹ is independently an alkyl group of 1 to 6 carbon atoms, anaryl group of 6 to 10 carbon atoms, a halogenated alkyl group of 1 to 6carbon atoms, or a halogenated aryl group of 6 to 10 carbon atoms; andsubscript a is an integer up to 20. Alternatively, subscript a is 0 to20, alternatively subscript a is 0 to 10; alternatively subscript a is 0to 5; and alternatively subscript a is 0 or 1. Alternatively, subscripta may be 2 to 10; alternatively subscript a is 2 to 5. Examples ofsuitable organohydrogensiloxane oligomers include1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3-tetramethyldisiloxane,1,1,3,3,5,5-hexaethyltrisiloxane, and 1,1,3,3-tetraethyldisiloxane.Alternatively, ingredient (A) may be 1,1,3,3-tetramethyldisiloxane.

When the organohydrogensiloxane oligomer of formula (VI) is used in themethod, the product comprises an alkoxy-functionalorganohydrogensiloxane oligomer produced of formula (VII):

where R¹ and subscripts a and c are as described above, D is a divalenthydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol% of D are linear divalent hydrocarbon groups.

In an alternative embodiment, ingredient (A) the organohydrogensiloxaneoligomer has unit formula (VIII): (HR¹ ₂SiO_(1/2))₃(R¹₂SiO_(2/2))_(q)(R¹SiO_(3/2)), where subscript q is 0 to 3. Thepolyorganohydrogensiloxane oligomer of this unit formula may haveformula (IX):

where R¹ is as described above. Examples of such organohydrogensiloxaneoligomers include siloxanes of formula (X):(Me₂HSiO_(1/2))₃(PrSiO_(3/2)), where Me represents a methyl group and Prrepresents a propyl group.

When the organohydrogensiloxane oligomer used for ingredient A) in themethod described above has unit formula (XII), the product comprises analkoxy-functional organohydrogensiloxane oligomer of formula (XIII)where formula (XIII) is:

where R¹ and subscript c are as described above, each D is independentlya divalent hydrocarbon group of 2 to 18 carbon atoms, with the provisothat >90 mol % of D are linear divalent hydrocarbon groups.

In an alternative embodiment of the invention, ingredient (A) theorganohydrogensiloxane oligomer may have unit formula (XIV): (HR¹₂SiO_(1/2))₂(R¹ ₂SiO_(2/2))_(q)(HR¹SiO_(2/2))_(r), where R¹ is asdescribed above, subscript q is 0 to 3, and subscript r is 0 to 3. Inthis embodiment, the organohydrogensiloxane oligomer may have formula(XV):

where R¹ is as described above. Examples of such organohydrogensiloxaneoligomers include 1,1,3,5,5-pentamethyltrisiloxane. In this embodiment,the product comprises an alkoxy-functional organohydrogensiloxaneoligomer of formula (XVI), formula (XVII), or a combination thereof,where formula (XVI) is

and formula (XVII) is

where R¹ and subscript c are as described above.

In an alternative embodiment ingredient (A) the organohydrogensiloxaneoligomer is cyclic. The cyclic organohydrogensiloxane oligomer may haveunit formula (XVIII): (R¹ ₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(s), where R¹ isas described above, subscript s 3, and subscript v 0. Alternatively,subscripts may be 3 to 14; alternatively 3 to 9, alternatively 3 to 6,alternatively 3 to 5, and alternatively 4. Alternatively, subscript vmay be 0 to 14; alternatively 0 to 9, alternatively 0 to 6,alternatively 0 to 5, and alternatively 0. When this cyclicorganohydrogensiloxane oligomer is used as ingredient (A), then theproduct may comprises an alkoxy-functional organohydrogensiloxaneoligomer of unit formula (XIX):

(R¹ ₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(t)

where R, R¹, D, and subscripts c and v are as described above, subscriptt is 0 or more, subscript u is 1 or more, and a quantity (t+u)=s.

Organohydrogensiloxane oligomers and methods for their preparation areknown in the art. For example, organohydrogensiloxane oligomers may beprepared, for example, by hydrolysis and condensation oforganohydrosilyl chlorides.

(B) Aliphatically Unsaturated Alkoxysilane

Ingredient (B) useful in the method described above is an aliphaticallyunsaturated alkoxysilane of formula (II):

where each R¹ is independently a monovalent hydrocarbon group or amonovalent halogenated hydrocarbon group (as described above), each R²is independently an aliphatically unsaturated hydrocarbon group, each R³is independently a monovalent hydrocarbon group, subscript c is 0 or 1.The aliphatically unsaturated hydrocarbon group for R² may be an alkenylgroup or an alkynyl group. Suitable alkenyl groups include vinyl, allyl,propenyl, butenyl and hexenyl; alternatively vinyl, allyl or hexenyl;and alternatively vinyl. The monovalent hydrocarbon group for R³ may bea monovalent hydrocarbon group as described above for R¹.

Ingredient (B) may comprise an aliphatically unsaturated alkoxysilaneexemplified by a dialkoxysilane, such as a dialkenyldialkoxysilane; atrialkoxysilane, such as an alkenyltrialkoxysilane; or a combinationthereof. Examples of suitable aliphatically unsaturated alkoxysilanesinclude vi nyltrimethoxysilane, al lyltriethoxysilane,allyltrimethoxysilane, vinyltriethoxysilane, hexenyltrimethoxysilane,vinylmethyldimethoxysilane, hexenylmethyldimethoxysilane,hexenyltriethoxysilane, and a combination thereof, and alternativelyvinyltrimethoxysilane. Aliphatically unsaturated silanes are known inthe art and are commercially available. For example,vinyltrimethoxysilane is commercially available as XIAMETER™ OFS-6300Silane and vinyltriethoxysilane is commercially available as XIAMETER™OFS-6518 Silane, both from Dow Silicones Corporation of Midland, Mich.,USA.

Ingredient (A) and ingredient (B) are present in relative molar amountsof ingredient (B):ingredient (A) of >1:1 to 1:1. Alternatively, (B):(A)ratio may range from 5:1 to 1:1, alternatively 2:1 to 1:1; andalternatively 1.5:1 to 1:1. Without wishing to be bound by theory, it isthought that a molar excess of ingredient (B) relative to ingredient (A)may favorably affect yield in the product.

(C) Hydrosilylation Reaction Catalyst

Ingredient (C) useful in the method and composition described herein isa hydrosilylation reaction catalyst. Hydrosilylation reaction catalystsare known in the art and are commercially available. Hydrosilylationreaction catalysts include platinum group metal catalysts. Suchhydrosilylation reaction catalysts can be (C-1) a metal selected fromplatinum, rhodium, ruthenium, palladium, osmium, and iridium.Alternatively, the hydrosilylation reaction catalyst may be (C-2) acompound of such a metal, for example,chloridotris(triphenylphosphane)rhodium(I) (Wilkinson's Catalyst), arhodium diphosphine chelate such as[1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or[1,2-bis(diethylphospino)ethane]dichlorodirhodium, chloroplatinic acid(Speier's Catalyst), chloroplatinic acid hexahydrate, platinumdichloride. Alternatively, the hydrosilylation reaction catalyst may be(C-3) a complex of the platinum group metal compound with a lowmolecular weight organopolysiloxane, or (C-4) the platinum group metalcompound microencapsulated in a matrix or coreshell type structure.Complexes of platinum with low molecular weight organopolysiloxanesinclude 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes withplatinum (Karstedt's Catalyst). Alternatively, the hydrosilylationcatalyst may comprise (C-5) the complex microencapsulated in a resinmatrix. Exemplary hydrosilylation reaction catalysts are described inU.S. Pat. Nos. 3,159,601; 3,220,972; 3,296,291; 3,419,593; 3,516,946;3,814,730; 3,989,668; 4,784,879; 5,036,117; and 5,175,325; and EP 0 347895 B. Microencapsulated hydrosilylation reaction catalysts and methodsof preparing them are known in the art, as exemplified in U.S. Pat. Nos.4,766,176 and 5,017,654. Alternatively, the hydrosilylation reactioncatalyst used herein may be a platinum catalyst. Platinum catalysts arecommercially available, for example, SYL-OFF™ 4000 Catalyst and SYL-OFF™2700 are available from Dow Silicones Corporation of Midland, Mich.,USA.

The amount of ingredient (C) used in step (1) of the method describedabove depends on various factors including the specificorganohydrogensiloxane oligomer selected for ingredient (A), thespecific alkoxysilane selected for ingredient (B), and the temperatureto which the mixture can be heated without boiling away theorganohydrogensiloxane oligomer selected for ingredient (A). However,the amount of ingredient (C) may be sufficient to provide a mass amountof platinum group metal of 1 parts per million (ppm) to 100 ppm,alternatively 5 ppm to 80 ppm, alternatively 5 ppm to 20 ppm based oncombined weights of ingredients (A) and (B). The method may optionallyfurther comprise deactivation or removal of the catalyst. However, withappropriate catalyst loading, the step of deactivation or removal of thecatalyst may be omitted.

(D) Hydro(Acyloxy)-Functional Silicon Compound

Ingredient (D) useful in the method described above is ahydro(acyloxy)-functional silicon compound of formula (III):

where each R⁵ is independently a monovalent hydrocarbon group of 1 to 18carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18carbon atoms, and R⁶ is a monovalent hydrocarbon group of 1 to 18 carbonatoms. Alternatively, R⁵ may have 1 to 6 carbon atoms. Alternatively, R⁵may be selected from the group consisting of methyl, ethyl, n-propyl,and isopropyl. Alternatively, R⁶ may have 1 to 6 carbon atoms.Alternatively, R⁶ may be selected from the group consisting of methyl,ethyl, n-propyl, isopropyl, and phenyl. Exemplary hydro(acyloxy)functional silicon compounds of formula (D-1) and methods for theirpreparation are disclosed, for example in U.S. Pat. No. 6,175,031.Alternatively, the hydro(acyloxy)-functional silicon compound may beselected from the group consisting of dimethylacetoxysilane,diethylacetoxysilane, methylphenylacetoxysilane,methylisopropylacetoxysilane, and diphenylacetoxysilane; alternativelydimethylacetoxysilane. The amount of hydro(acyloxy)-functional siliconcompound is >0 to 40 mole %, alternatively >0 to 20 mole %, based on theamount of starting material (A).

Ingredient (E) Sorbent

Ingredient (E) is a sorbent. For purposes of this application, the term“sorbent” and its derivatives, means a material capable of absorbingand/or adsorbing; alternatively adsorbing, and alternatively absorbing.Alternatively, sorbent can include a material capable of both absorbingand adsorbing. The sorbent may be selected from the group consisting of:(E-1) an activated carbon, (E-2) an ion exchange resin, (E-3) a compoundof formula NR⁸ _(x)R⁹ _(y)R¹⁰ _((3-x-y)), where R⁸, R⁹, and R¹⁹ are eachindependently selected from the group consisting of a hydrogen atom anda monovalent hydrocarbon group of 1 to 18 carbon atoms, subscript x is 0to 3, subscript y is 0 to 3, and a quantity (x+y)≤3; (E-4) a compound offormula

where R¹¹ is selected from the group consisting of a hydrogen atom and amonovalent hydrocarbon group of 1 to 18 carbon atoms, and R¹² is adivalent hydrocarbon group of 1 to 18 carbon atoms; and (E-5) acombination of two or more of (E-1) to (E-4).

Alternatively, the sorbent may be (E-1) an activated carbon. Theactivated carbon may be a bituminous coal based activated carbon forexample, Filtrasorb™ 600 which is commercially available from CalgonCarbon Corporation of Pittsburgh, Pa., USA or a lignite based activatedcarbon such as, Darco™ 12×40 which is commercially available from CabotCorporation of Boston, Mass., USA. This sorbent may be loaded at 1% to30%, alternatively 1% to 10%, alternatively 5% to 30% and alternatively10% to 30%, based on weight of Ingredient (A).

Alternatively, the sorbent may be (E-2) an ion exchange resin. Suitableion exchange resins are known in the art and are commercially available.For example, the ion exchange resin may be a weak base anion exchangeresin, such as AMBERLITE™ IRA-67, which is commercially available fromDuPont de Nemours Inc. of Wilmington, Del., USA; and Amberlyst A21. Thissorbent may be loaded at 1% to 40% based on weight of Ingredient (A).

Alternatively, the sorbent may have formula (E-3): NR⁸ _(x)R⁹ _(y)R¹⁰_((3-x-y)), where R⁸, R⁹, and R¹⁰ are each independently selected fromthe group consisting of a hydrogen atom and a monovalent hydrocarbongroup of 1 to 18 carbon atoms, subscript x is 0 to 3, subscript y is 0to 3, and a quantity (x+y) 3. Alternatively, the absorbent may beammonia (NH₃). This sorbent may be loaded at 0.5% to 50%, based onweight of Ingredient (A), alternatively 0.5% to 20% on the same basis.

Alternatively, the sorbent may have formula (E-4):

where R¹¹ is selected from the group consisting of a hydrogen atom and amonovalent hydrocarbon group of 1 to 18 carbon atoms, and R¹² is adivalent hydrocarbon group of 1 to 18 carbon atoms. Examples of thesorbent of formula (E-4) include piperidine, 1-methylpiperidine,pyrrolidine, 1-methylpyrrolidine. This sorbent may be loaded at 1% to50%, based on weight of Ingredient (A).

Alternatively, the sorbent may be a combination of any two or more of(E-1), (E-2), (E-3), and (E-4).

Ingredient (F) Compound

Ingredient (F) is a compound of formula (XXII): HOR⁷, where R⁷ is ahydrogen atom or a monovalent hydrocarbon group of 1 to 18 carbon atoms.Alternatively, R⁷ is a hydrogen atom or an alkyl group of 1 to 18 carbonatoms, alternatively 1 to 12 carbon atoms, and alternatively 1 to 6carbon atoms. Alternatively, each R⁷ is selected from the groupconsisting of hydrogen and methyl. The compound may be selected from thegroup consisting of water and methanol. The amount of Ingredient (F) maybe 0.5% to 50%, alternatively 1% to 30%, based on weight of Ingredient(A).

Method Step 1)

Step 1) in the method for making the alkoxy-functionalorganohydrogensiloxane oligomer comprises mixing ingredients comprisingingredients (A), (B), (C), and (D), as described above. Step 1) of themethod described herein may be performed at 1 atmosphere of pressure orhigher. Alternatively, the method may be performed at 1 atmosphere to1.5 atmosphere. Step 1) may be performed at 0° C. to 150° C.,alternatively 50° C. to 150° C., alternatively 60° C. to 150° C., andalternatively 50° C. to 100° C. The temperature for heating in step 1)depends on various factors including the pressure selected, however,heating may be performed at least 70° C. to ensure the reaction proceedsquickly enough to be practical. The upper limit for temperature duringheating is not critical and depends on the ingredients selected, i.e.,the upper limit should be such that the ingredients do not vaporize outof the reactor selected for performing the method. Alternatively,heating may be from 70° C. to 150° C., alternatively 70° C. to 100° C.

The ingredients in step 1) of the method described above form a mixture,which may be homogeneous or heterogeneous. One or more additionalingredients, i.e., in addition to ingredients (A), (B), (C), and (D)described above, may optionally be used in the method. The additionalingredient, when present, may be (G) a solvent.

Ingredient (G) is a solvent that may be added to the mixture used instep 1) of the method described herein. One or more of ingredients (A),(B), (C) and/or (D) may be provided in a solvent. For example,ingredient (C) the catalyst may be dissolved in a solvent that is addedto the mixture in step 1). The solvent may facilitate contacting ofreactants and catalyst, flow of the mixture and/or introduction ofcertain ingredients, such as the catalyst. Solvents used herein arethose that help fluidize the ingredients of the mixture but essentiallydo not react with any of these ingredients. Solvents may be selectedbased on solubility the ingredients in the mixture and volatility. Thesolubility refers to the solvent being sufficient to dissolveingredients of the mixture. Volatility refers to vapor pressure of thesolvent. If the solvent is too volatile (having too high vapor pressure)the solvent may not remain in solution during heating. However, if thesolvent is not volatile enough (too low vapor pressure) the solvent maybe difficult to remove from the product or isolate from thealkoxy-functional organohydrogensiloxane oligomer.

The solvent may be an organic solvent. The organic solvent can be ahydrocarbon compound such as a saturated hydrocarbon or an aromatichydrocarbon. Suitable saturated hydrocarbons include hexane,cyclohexane, heptane, octane, and dodecane. Suitable aromatichydrocarbons include benzene, toluene, or xylene, or a combinationthereof. Ingredient (G) may be one solvent. Alternatively, ingredient(G) may comprise two or more different solvents.

The amount of solvent can depend on various factors including thespecific solvent selected and the amount and type of other ingredientsselected for the mixture. However, the amount of solvent may range from0% to 99%, or when present, 1% to 99%, and alternatively 2% to 50%,based on the weight of the mixture.

Optional Step) Distilling the Reaction Product of Step 1)

The reaction product of step 1) may optionally be distilled before step2). Distillation may be performed at 150° C. to 250° C. under reducedpressure. Pressure may be reduced to 0 to 5 mmHg, alternatively 0 to 2mmHg. Distillation may remove all or a portion of any unreacted startingmaterials, and solvent, if used. However, distillation before step 2) isnot required.

Alternatively, step 2) may be performed directly after step 1), i.e.,without a purification step such as distillation after step 1) andbefore step 2).

Step 2) Treating the Product

The method for preparing the product comprising the alkoxy-functionalorganohydrogensiloxane oligomer further comprises: 2) treating thereaction product prepared in step 1) with a treating agent comprising(E) the sorbent, and (F) the compound of formula (XXII): HOR⁷, where R⁷is a hydrogen atom or a monovalent hydrocarbon group of 1 to 18 carbonatoms. Treating may be done by any convenient means, for example, thetreating agent may be added to the reaction product prepared in step 1)with mixing at RT. The reaction product of step 1) may be combined withIngredients (E) and (F) with stirring at RT. Time for treating in step2) may be 1 h to 24 h depending on the selection of sorbent. Forexample, treating may be performed for 10 h to 24 h if the sorbent is asolid at RT. Alternatively, treating may be performed for 1 h to 3 hwhen the sorbent is ammonia or an amine sorbents.

The method further comprises step 3): distilling the product of step 2),thereby recovering the alkoxy-functional organohydrogensiloxaneoligomer. Distilling may be performed by any convenient means, e.g.,with at RT or with heating and/or under vacuum, or a combinationthereof. Conditions selected are sufficient to remove Ingredient (F) andany side product such as that of formula R⁶COOH, where R⁶ is asdescribed above. For example, for the promoter, dimethylacetoxysilane,the conditions in step 3) were 30 mmHg at 25° C.

The (crude) reaction product of step 1) comprises the β-adduct compoundalkoxy-functional organohydrogensiloxane oligomer, which is useful forfunctionalization of polyorganosiloxanes, including oligomers and longerchain polymers, containing aliphatically unsaturated functionality. Forexample, a hydrosilylation reaction of the SiH group in thealkoxy-functional organohydrogensiloxane oligomer of formula (IV) withan aliphatically unsaturated group bonded to silicon in apolyorganosiloxane (such as a polydiorganosiloxane having analiphatically unsaturated terminal group) can produce analkoxy-functional polyorganosiloxane. The polyorganosiloxane having analiphatically unsaturated terminal group may have unit formula (XXIII):(R¹⁷R¹⁸SiO_(1/2))_(e)(R¹⁷R¹⁸SiO_(2/2))_(f)(R¹⁷SiO_(3/2))_(g)(SiO_(4/2))_(h),where each R¹⁷ is independently a hydrogen atom, an alkyl group, an arylgroup, a halogenated alkyl group, or a halogenated aryl group (such asthose described above for R¹), and each R¹⁸ is independently analiphatically unsaturated hydrocarbon group such as an alkenyl groupexemplified by alkenyl groups such as vinyl, allyl, butenyl, andhexenyl; and alkynyl groups such as ethynyl and propynyl. Subscript e isan integer of 0 or more, subscript f is an integer of 0 or more,subscript g is an integer of 0 or more, and subscript h is an integer of0 or more, with the proviso that a quantity (f+g)>1. Alternatively, thepolyorganosiloxane may be a polydiorganosiloxane. Thepolydiorganosiloxane having aliphatically unsaturated terminal groupsmay have formula (XXIV): R¹⁷ ₂R¹⁸SiO(R¹⁷ ₂SiO)_(d)SiR¹⁷ ₂R¹⁸.

In formula (XVIII), R¹⁷ and R¹⁸ are as described above. Subscript d maybe 0 or a positive number. Alternatively, each R¹⁷ may be an alkyl groupor an aryl group as described above for R¹. Alternatively, subscript dhas an average value of at least 2. Alternatively subscript d may have avalue ranging from 2 to 2000.

The compound of formula (XXIV) may comprise a polydiorganosiloxane suchas i) dimethylvinylsiloxy-terminated polydimethylsiloxane, ii)dimethylvinylsiloxy-terminatedpoly(dimethylsiloxane/methylphenylsiloxane), iii)dimethylvinylsiloxy-terminated poly(dimethylsiloxane/diphenylsiloxane),iv) phenyl,methyl,vinyl-siloxy-terminated polydimethylsiloxane, or v)dimethylhexenylsiloxy-terminated polydimethylsiloxane. Thealkoxy-functional polyorganosiloxane may be produced by combining theproduct including the β-adduct compound alkoxy-functionalorganohydrogensiloxane oligomer with a polydiorganosiloxane of formula(XXIV) as described above.

The hydrosilylation reaction to prepare the polyalkoxy-functionalpolyorganosiloxane may be performed by a method comprising:

combining starting materials comprising(a) the product comprising the β-adduct compound alkoxy-functionalorganohydrogensiloxane oligomer as described above,(b) the polyorganosiloxane having at least one aliphatically unsaturatedsilicon bonded group per molecule as described above, and(c) a hydrosilylation catalyst which may be the same as, or differentfrom, the hydrosilylation reaction catalyst used in step 1).

The polyalkoxy-functional polyorganosiloxanes produced by thehydrosilylation of described above may have formula: (XXV): R¹⁷₂R¹⁹SiO(R¹⁷ ₂SiO)_(d)SiR¹⁷ ₂R¹⁹, where R¹⁷ and subscript d are asdescribed above, and each R¹⁹ is polyalkoxy-functional group. In formula(XXV), >90 mol % of R¹⁹ may be β-adduct. Alternatively, in formula(XXV), >90 mol % to 100 mol % of R¹⁹ may be β-adduct groups.Alternatively, in formula (XXV), 92% to <100%% of R¹⁹ may be β-adductgroups.

For example, when (b) the polyorganosiloxane having aliphaticallyunsaturated terminal groups is a polydiorganosiloxane of formula (XXVI):

where subscript n is 1 to 2,000; the polyalkoxy-functionalpolyorganosiloxane may have formula (XXVII):

where each D¹ is independently a divalent hydrocarbon group; where R¹,R², D and subscript c are as described above.

Alternatively, the polyalkoxy-functional polyorganosiloxane may haveformula (XXVIII):

where each D¹ is independently a divalent hydrocarbon group; where R¹,R², D and subscript c are as described above.

The polyalkoxy-functional polyorganosiloxanes, such aspolyalkoxy-functional polydimethylsiloxanes, prepared as described abovecan be used in any application that utilizes reactivity of the alkoxygroups.

For example, the polyalkoxy-functional polyorganosiloxane prepared asdescribed above is useful in condensation reaction curable compositions,such as sealant compositions. Suitable condensation reaction curablecompositions can be prepared by mixing starting materials comprising:

(i) the alkoxy-functional polyorganosiloxane prepared as describedabove, and

(ii) condensation reaction catalyst. Without wishing to be bound bytheory, it thought that a condensation reaction curable compositionincluding (i) the polyalkoxy-functional polyorganosiloxane will curefaster than a similar condensation reaction curable compositioncontaining a different polyalkoxy-functional polyorganosiloxane(prepared using a conventional endblocker having higher branched isomercontent)

Starting material (ii) is a condensation reaction catalyst. Suitablecondensation reaction catalysts include tin catalysts and titaniumcatalysts. Suitable tin catalysts include organotin compounds where thevalence of the tin is either +4 or +2, i.e., Tin (IV) compounds or Tin(II) compounds. Examples of tin (IV) compounds include stannic salts ofcarboxylic acids such as dibutyl tin dilaurate, dimethyl tin dilaurate,di-(n-butyl)tin bis-ketonate, dibutyl tin diacetate, dibutyl tinmaleate, dibutyl tin diacetylacetonate, dibutyl tin dimethoxide,carbomethoxyphenyl tin tris-uberate, dibutyl tin dioctanoate, dibutyltin diformate, isobutyl tin triceroate, dimethyl tin dibutyrate,dimethyl tin di-neodeconoate, dibutyl tin di-neodeconoate, triethyl tintartrate, dibutyl tin dibenzoate, butyltintri-2-ethylhexanoate, dioctyltin diacetate, tin octylate, tin oleate, tin butyrate, tin naphthenate,dimethyl tin dichloride, a combination thereof, and/or a partialhydrolysis product thereof. Tin (IV) compounds are known in the art andare commercially available, such as Metatin™ 740 and Fascat™ 4202 fromAcima Specialty Chemicals of Switzerland, Europe, which is a businessunit of The Dow Chemical Company. Examples of tin (II) compounds includetin (II) salts of organic carboxylic acids such as tin (II) diacetate,tin (II) dioctanoate, tin (II) diethylhexanoate, tin (II) dilaurate,stannous salts of carboxylic acids such as stannous octoate, stannousoleate, stannous acetate, stannous laurate, stannous stearate, stannousnaphthanate, stannous hexanoate, stannous succinate, stannous caprylate,and a combination thereof. Exemplary titanium catalysts include titaniumesters such as tetra-n-butyltitanate tetraisopropyltitanate,tetra-2-ethylhexyltitanate, tetraphenyltitanate, triethanolaminetitanate, organosiloxytitanium compounds, and dicarbonyl titaniumcompounds, such as titanium ethyl acetoacetate andbis(acetoacetonyl)-diisopropoxy titanium (IV). A titanium catalyst maybe used when the composition will be formulated as a room temperaturevulcanizing sealant composition. The amount of condensation reactioncatalyst depends on various factors including the amount of startingmaterial (i) and the types and amounts of any additional startingmaterials added to the composition, however the amount of condensationreaction catalyst may be 0.2 to 6, alternatively 0.5 to 3, parts byweight based on the weight of starting material (i).

The condensation reaction curable composition may further comprise oneor more additional ingredients distinct from ingredients (i) and (ii).Suitable additional ingredients are exemplified by (iii) a filler; (iv)a filler treating agent; (v) a crosslinker; (vi) a surface modifier,(vii) a drying agent; (viii) an extender, a plasticizer, or acombination thereof; (ix) a biocide; (x) a flame retardant; (xi) a chainlengthener; (xii) an endblocker; (xiii) a nonreactive binder; (xiv) ananti-aging additive; (xv) a water release agent; (xvi) a pigment; (xvii)a rheological additive; (xviii) a vehicle (such as a solvent and/or adiluent); (xix) a tackifying agent; (xx) a corrosion inhibitor; and acombination of two or more thereof. These additional ingredients andtheir amounts for use in a condensation reaction curable composition areexemplified by those disclosed, for example, in U.S. Pat. No. 9,156,948.

Starting material (iii) that may be added to the composition is afiller. The filler may comprise a reinforcing filler, an extendingfiller, or a combination thereof. For example, the composition mayoptionally further comprise ingredient (iii-1), a reinforcing filler,which when present may be added in an amount ranging from 0.1% to 95%,alternatively 1% to 60%, based on the weight of the composition. Theexact amount of starting material (iii-1) depends on various factorsincluding the form of the reaction product of the composition andwhether any other fillers are added. Examples of suitable reinforcingfillers include precipitated calcium carbonates and reinforcing silicafillers such as fume silica, silica aerogel, silica xerogel, andprecipitated silica. Suitable precipitated calcium carbonates includeWinnofil™ SPM from Solvay and Ultrapflex™ from Specialty Minerals, Inc.Fumed silicas are known in the art and commercially available; e.g.,fumed silica sold under the name CAB-O-SIL™ by Cabot Corporation ofMassachusetts, U.S.A.

The composition may optionally further comprise starting material(iii-2) an extending filler in an amount ranging from 0.1% to 95%,alternatively 1% to 60%, and alternatively 1% to 20%, based on theweight of the composition. Examples of extending fillers include crushedquartz, aluminium oxide, magnesium oxide, ground calcium carbonate, zincoxide, talc, diatomaceous earth, iron oxide, clays, mica, chalk,titanium dioxide, zirconia, sand, carbon black, graphite, or acombination thereof. Extending fillers are known in the art andcommercially available; such as a ground quartz sold under the nameMIN—U-SIL™ by U.S. Silica of Berkeley Springs, W. Va. Examples ofextending calcium carbonates include CS-11 from Imerys, G3T from Huber,and Omyacarb 2T from Omya.

The composition may optionally further comprise starting material (iv) atreating agent. The amount of starting material (iv) can vary dependingon factors such as the type of treating agent selected and the type andamount of particulates to be treated, and whether the particulates aretreated before being added to the composition, or whether theparticulates are treated in situ. However, starting material (iv) may beused in an amount ranging from 0.01% to 20%, alternatively 0.1% to 15%,and alternatively 0.5% to 5%, based on the weight of the composition.Particulates, such as the filler, the physical drying agent, certainflame retardants, certain pigments, and/or certain water release agents,when present, may optionally be surface treated with starting material(iv). Particulates may be treated with starting material (iv) beforebeing added to the composition, or in situ. Starting material (iv) maycomprise an alkoxysilane, an alkoxy-functional oligosiloxane, a cyclicpolyorganosiloxane, a hydroxyl-functional oligosiloxane such as adimethyl siloxane or methyl phenyl siloxane, or a fatty acid. Examplesof fatty acids include stearates such as calcium stearate.

Some representative organosilicon filler treating agents that can beused as starting material (iv) include compositions normally used totreat silica fillers such as organochlorosilanes, organosiloxanes,organodisilazanes such as hexaalkyl disilazane, and organoalkoxysilanessuch as C₆H₁₃Si(OCH₃)₃, C₈H₁₇Si(OC₂H₅)₃, C₁₀H₂₁Si(OCH₃)₃,C₁₂H₂₅Si(OCH₃)₃, C₁₄H₂₉Si(OC₂H₅)₃, and C₆H₅CH₂CH₂Si(OCH₃)₃. Othertreating agents that can be used include alkylthiols, fatty acids,titanates, titanate coupling agents, zirconate coupling agents, andcombinations thereof.

Alternatively, starting material (iv) may comprise an alkoxysilanehaving the formula (XXIX): R¹³ _(p)Si(OR¹⁴)_((4-p)), where subscript pmay have a value ranging from 1 to 3, alternatively subscript p is 3.Each R¹³ is independently a monovalent organic group, such as amonovalent hydrocarbon group of 1 to 50 carbon atoms, alternatively 8 to30 carbon atoms, alternatively 8 to 18 carbon atoms. R¹³ is exemplifiedby alkyl groups such as hexyl, octyl, dodecyl, tetradecyl, hexadecyl,and octadecyl; and aromatic groups such as benzyl and phenylethyl. R¹³may be saturated or unsaturated, and branched or unbranched.Alternatively, R¹³ may be saturated and unbranched.

Each R¹⁴ is independently a saturated hydrocarbon group of 1 to 4 carbonatoms, alternatively 1 to 2 carbon atoms. Starting material (iv) isexemplified by hexyltrimethoxysilane, octyltriethoxysilane,decyltrimethoxysilane, dodecyltrimethoxysilane,tetradecyltrimethoxysilane, phenylethyltrimethoxysilane,octadecyltrimethoxysilane, octadecyltriethoxysilane, and combinationsthereof.

Alkoxy-functional oligosiloxanes may also be used as treating agents.For example, suitable alkoxy-functional oligosiloxanes include those ofthe formula (XXX): (R²⁰O)_(q)Si(OSiR²¹ ₂R²²)_((4-q)). In this formula,subscript q is 1, 2 or 3, alternatively subscript q is 3. Each R²⁰ maybe an alkyl group. Each R²¹ may be independently selected from asaturated or an unsaturated monovalent hydrocarbon group of 1 to 10carbon atoms. Each R²² may be independently selected from a saturated oran unsaturated monovalent hydrocarbon group having at least 10 carbonatoms. Suitable alkoxy-functional oligosiloxanes and methods for theirpreparation are disclosed, for example, in U.S. Pat. No. 6,376,635.

Alternatively, a polyorganosiloxane capable of hydrogen bonding isuseful as a treating agent. This strategy to treating surface of afiller takes advantage of multiple hydrogen bonds, either clustered ordispersed or both, as the means to tether the compatibilization moietyto the filler surface. The polyorganosiloxane capable of hydrogenbonding has an average, per molecule, of at least one silicon-bondedgroup capable of hydrogen bonding. The group may be selected from: anorganic group having multiple hydroxyl functionalities or an organicgroup having at least one amino functional group. The polyorganosiloxanecapable of hydrogen bonding means that hydrogen bonding is the primarymode of attachment for the polyorganosiloxane to a filler. Thepolyorganosiloxane may be incapable of forming covalent bonds with thefiller. The polyorganosiloxane may be free of condensable silyl groupse.g., silicon bonded alkoxy groups, silazanes, and silanols. Thepolyorganosiloxane capable of hydrogen bonding may be selected from thegroup consisting of a saccharide-siloxane polymer, an amino-functionalpolyorganosiloxane, and a combination thereof. Alternatively, thepolyorganosiloxane capable of hydrogen bonding may be asaccharide-siloxane polymer.

Starting material (v) is a crosslinker. Starting material (v) maycomprise a silane crosslinker having hydrolyzable groups or partial orfull hydrolysis products thereof. Starting material (v) has an average,per molecule, of greater than two substituents reactive with the alkoxygroups on starting material (i). Examples of suitable silanecrosslinkers for starting material (v) may have general formula (XXXI):R¹⁴ _(k)Si(R¹³)_((4-k)), where each R¹⁴ is independently a monovalenthydrocarbon group such as an alkyl group; each R¹³ is a hydrolyzablesubstituent, for example, a halogen atom, an acetamido group, an acyloxygroup such as acetoxy, an alkoxy group, an amido group, an amino group,an aminoxy group, a hydroxyl group, an oximo group, a ketoximo group, ora methylacetamido group; and each instance of subscript k may be 0, 1,2, or 3. For starting material (v), subscript k has an average valuegreater than 2. Alternatively, subscript k may have a value ranging from3 to 4. Alternatively, each R¹³ may be independently selected fromhydroxyl, alkoxy, acetoxy, amide, or oxime. Alternatively, startingmaterial (v) may be selected from an acyloxysilane, an alkoxysilane, aketoximosilane, and an oximosilane.

Starting material (v) may comprise an alkoxysilane exemplified by adialkoxysilane, such as a dialkyldialkoxysilane; a trialkoxysilane, suchas an alkyltrialkoxysilane; a tetraalkoxysilane; or partial or fullhydrolysis products thereof, or another combination thereof. Examples ofsuitable trialkoxysilanes include methyltrimethoxysilane,methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,isobutyltrimethoxysilane, isobutyltriethoxysilane, and a combinationthereof, and alternatively methyltrimethoxysilane. Examples of suitabletetraalkoxysilanes include tetraethoxysilane. The amount of thealkoxysilane that is used in the composition may range from 0.5 to 15,parts by weight per 100 parts by weight of starting material (i).

Starting material (v) may comprise an acyloxysilane, such as anacetoxysilane. Acetoxysilanes include a tetraacetoxysilane, anorganotriacetoxysilane, a diorganodiacetoxysilane, or a combinationthereof. The acetoxysilane may contain alkyl groups such as methyl,ethyl, propyl, isopropyl, butyl, and tertiary butyl; alkenyl groups suchas vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, orxylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinatedalkyl groups such as 3,3,3-trifluoropropyl. Exemplary acetoxysilanesinclude, but are not limited to, tetraacetoxysilane,methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane,propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane,octyltriacetoxysilane, dimethyldiacetoxysilane, phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyldiacetoxysilane, tetraacetoxysilane, and combinations thereof.Alternatively, starting material (v) may compriseorganotriacetoxysilanes, for example mixtures comprisingmethyltriacetoxysilane and ethyltriacetoxysilane. The amount of theacetoxysilane that is used in the curable silicone composition may rangefrom 0.5 to 15 parts by weight per 100 parts by weight of startingmaterial (i); alternatively 3 to 10 parts by weight of acetoxysilane per100 parts by weight of starting material (i).

Examples of silanes suitable for starting material (v) containing bothalkoxy and acetoxy groups that may be used in the composition includemethyldiacetoxymethoxysilane, methylacetoxydimethoxysilane,vinyldiacetoxymethoxysilane, vi nylacetoxydimethoxysilane,methyldiacetoxyethoxysilane, metylacetoxydiethoxysilane, andcombinations thereof.

Aminofunctional alkoxysilanes suitable for starting material (v) areexemplified by H₂N(CH₂)₂Si(OCH₃)₃, H₂N(CH₂)₂Si(OCH₂CH₃)₃,H₂N(CH₂)₃Si(OCH₃)₃, H₂N(CH₂)₃Si(OCH₂CH₃)₃, CH₃NH(CH₂)₃Si(OCH₃)₃,CH₃NH(CH₂)₃Si(OCH₂CH₃)₃, CH₃NH(CH₂)₅Si(OCH₃)₃, CH₃NH(CH₂)₅Si(OCH₂CH₃)₃,H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, H₂N(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃,H₂N(CH₂)₂SiCH₃(OCH₃)₂, H₂N(CH₂)₂SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₅SiCH₃(OCH₃)₂,CH₃NH(CH₂)₅SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, and a combination thereof.

Suitable oximosilanes for starting material (v) includealkyltrioximosilanes such as methyltrioximosilane, ethyltrioximosilane,propyltrioximosilane, and butyltrioximosilane; alkoxytrioximosilanessuch as methoxytrioximosilane, ethoxytrioximosilane, andpropoxytrioximosilane; or alkenyltrioximosilanes such aspropenyltrioximosilane or butenyltrioximosilane; alkenyloximosilanessuch as vinyloximosilane; alkenylalkyldioximosilanes such as vinylmethyl dioximosilane, vinyl ethyldioximosilane, vinylmethyldioximosilane, or vinylethyldioximosilane; or combinationsthereof.

Suitable ketoximosilanes for starting material (v) include methyltris(dimethylketoximo)silane, methyl tris(methylethylketoximo)silane,methyl tris(methylpropylketoximo)silane, methyltris(methylisobutylketoximo)silane, ethyl tris(dimethylketoximo)silane,ethyl tris(methylethylketoximo)silane, ethyltris(methylpropylketoximo)silane, ethyltris(methylisobutylketoximo)silane, vinyl tris(dimethylketoximo)silane,vinyl tris(methylethylketoximo)silane, vinyltris(methylpropylketoximo)silane, vinyltris(methylisobutylketoximo)silane, tetrakis(dimethylketoximo)silane,tetrakis(methylethylketoximo)silane,tetrakis(methylpropylketoximo)silane,tetrakis(methylisobutylketoximo)silane,methylbis(dimethylketoximo)silane, methylbis(cyclohexylketoximo)silane,triethoxy(ethylmethylketoxime)silane,diethoxydi(ethylmethylketoxime)silane,ethoxytri(ethylmethylketoxime)silane,methylvinylbis(methylisobutylketoximo)silane, or a combination thereof.

Alternatively, starting material (v) may be polymeric. For example,starting material (v) may comprise a disilane such asbis(triethoxysilyl)hexane), 1,4-bis[trimethoxysilyl(ethyl)]benzene, andbis[3-(triethoxysilyl)propyl] tetrasulfide.

Starting material (v) can be one single crosslinker or a combinationcomprising two or more crosslinkers that differ in at least one of thefollowing properties: hydrolyzable substituents and other organic groupsbonded to silicon, and when a polymeric crosslinker is used, siloxaneunits, structure, molecular weight, and sequence.

Starting material (vi) is an adhesion promoter. Suitable adhesionpromoters for starting material (vi) may comprise a hydrocarbonoxysilanesuch as an alkoxysilane, a combination of an alkoxysilane and ahydroxy-functional polyorganosiloxane, an aminofunctional silane, amercaptofunctional silane, or a combination thereof. Adhesion promotersare known in the art and may comprise silanes having the formula(XXXII): R²⁴ _(t)R²⁵ _(u)Si(OR²⁶)_(4-(t+u)) where each R²⁴ isindependently a monovalent organic group having at least 3 carbon atoms;R²⁵ contains at least one SiC bonded substituent having anadhesion-promoting group, such as amino, epoxy, mercapto or acrylategroups; each R²⁶ is independently a saturated hydrocarbon group;subscript t has a value ranging from 0 to 2; subscript u is either 1 or2; and the sum of (t+u) is not greater than 3. Saturated hydrocarbongroups for R²⁶ may be, for example, an alkyl group of 1 to 4 carbonatoms, alternatively 1 to 2 carbon atoms. R²⁶ is exemplified by methyl,ethyl, propyl, and butyl. Alternatively, the adhesion promoter maycomprise a partial condensate of the above silane. Alternatively, theadhesion promoter may comprise a combination of an alkoxysilane and ahydroxy-functional polyorganosiloxane.

Alternatively, the adhesion promoter may comprise an unsaturated orepoxy-functional compound. The adhesion promoter may comprise anunsaturated or epoxy-functional alkoxysilane. For example, thefunctional alkoxysilane can have the formula (XXXIII): R²⁷_(v)Si(OR²⁸)_((4-v)), where subscript v is 1, 2, or 3, alternativelysubscript v is 1. Each R²⁷ is independently a monovalent organic groupwith the proviso that at least one R²⁷ is an unsaturated organic groupor an epoxy-functional organic group. Epoxy-functional organic groupsfor R²⁷ are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl.Unsaturated organic groups for R²⁷ are exemplified by3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalenthydrocarbon groups such as vinyl, allyl, hexenyl, undecylenyl. Each R²⁸is independently a saturated hydrocarbon group of 1 to 4 carbon atoms,alternatively 1 to 2 carbon atoms. R²⁸ is exemplified by methyl, ethyl,propyl, and butyl.

Examples of suitable epoxy-functional alkoxysilanes include3-glycidoxypropyltrimethoxysilane, 3-g lycidoxypropyltriethoxysilane,(epoxycyclohexyl)ethyldimethoxysilane,(epoxycyclohexyl)ethyldiethoxysilane and combinations thereof. Examplesof suitable unsaturated alkoxysilanes include vinyltrimethoxysilane,allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane,undecylenyltrimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane,3-methacryloyloxypropyl triethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyl triethoxysilane, and combinationsthereof.

Alternatively, the adhesion promoter may comprise an epoxy-functionalsiloxane such as a reaction product of a hydroxy-terminatedpolyorganosiloxane with an epoxy-functional alkoxysilane, as describedabove, or a physical blend of the hydroxy-terminated polyorganosiloxanewith the epoxy-functional alkoxysilane. The adhesion promoter maycomprise a combination of an epoxy-functional alkoxysilane and anepoxy-functional siloxane. For example, the adhesion promoter isexemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and areaction product of hydroxy-terminated methylvinylsiloxane with3-glycidoxypropyltrimethoxysilane, or a mixture of3-glycidoxypropyltrimethoxysilane and a hydroxy-terminatedmethylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilaneand a hydroxy-terminated methylvinyl/dimethylsiloxane copolymer.

Alternatively, the adhesion promoter may comprise an aminofunctionalsilane, such as an aminofunctional alkoxysilane exemplified byH₂N(CH₂)₂Si(OCH₃)₃, H₂N(CH₂)₂Si(OCH₂CH₃)₃, H₂N(CH₂)₃Si(OCH₃)₃,H₂N(CH₂)₃Si(OCH₂CH₃)₃, CH₃NH(CH₂)₃Si(OCH₃)₃, CH₃NH(CH₂)₃Si(OCH₂CH₃)₃,CH₃NH(CH₂)₅Si(OCH₃)₃, CH₃NH(CH₂)₅Si(OCH₂CH₃)₃, H₂N(CN₂)₂N H₂)₃Si(OCH₃)₃,H₂N(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃, CH₃NH(CH₂)₂NH(CH₂)₃Si(OCH₃)₃,CH₃NH(CH₂)₂N H₂)₃Si(OCH₂CH₃)₃, C₄H₉NH(CH₂)₂NH₂)₃Si(OCH₃)₃,C₄H₉NH(CH₂)₂NH(CH₂)₃Si(OCH₂CH₃)₃, H₂N(CH₂)₂SiCH₃(OCH₃)₂,H₂N(CH₂)₂SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₅SiCH₃(OCH₃)₂,CH₃NH(CH₂)₅SiCH₃(OCH₂CH₃)₂, H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,H₂N(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,CH₃NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂, C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂,C₄H₉NH(CH₂)₂NH(CH₂)₃SiCH₃(OCH₂CH₃)₂,N-(3-(trimethoxysilyl)propyl)ethylenediamine, and a combination thereof.

Alternatively, the adhesion promoter may comprise a mercaptofunctionalalkoxysilane, such as 3-mercaptopropyltrimethoxysilane or3-mercaptopropyltriethoxysilane.

The exact amount of starting material (vi) depends on various factorsincluding the type of adhesion promoter selected and the end use of thecomposition and its reaction product. However, starting material (vi),when present, may be added to the composition in an amount ranging from0.01 to 50 weight parts based on the weight of the composition,alternatively 0.01 to 10 weight parts, and alternatively 0.01 to 5weight parts. Starting material (vi) may be one adhesion promoter.Alternatively, starting material (vi) may comprise two or more differentadhesion promoters that differ in at least one of the followingproperties: structure, viscosity, average molecular weight, polymerunits, and sequence.

When selecting ingredients for the condensation reaction curablecomposition described above, there may be overlap between types ofstarting materials because certain starting materials described hereinmay have more than one function. For example, certain alkoxysilanes maybe useful as filler treating agents, as adhesion promoters, and ascrosslinkers.

Alternatively, the crosslinker, the filler, and the adhesion promotermay each be present in the composition. In this embodiment, thecrosslinker may comprise an alkyl trialkoxysilane, such asmethyltrimethoxysilane; the filler may comprise an extending filler suchas calcium carbonate; and the adhesion promoter may comprise analkoxysilane other than the crosslinker, such asN-(3-(trimethoxysilyl)propyl)ethylenediamine,3-mercaptopropyltrimethoxysilane, or both

The composition described above may be prepared as a one partcomposition, for example, by combining all ingredients by any convenientmeans, such as mixing. For example, a one-part composition may be madeby optionally combining (e.g., premixing) (i) the alkoxy-functionalpolyorganosiloxane with all or part of (iii) the filler, when present;and mixing this with a pre-mix comprising the catalyst (ii) and, whenpresent (v) the crosslinker. Other additives such as an anti-agingadditive and a pigment may be added to the mixture at any desired stage.A final mixing step may be performed under substantially anhydrousconditions, and the resulting compositions are generally stored undersubstantially anhydrous conditions, for example in sealed containers,until ready for use.

Alternatively, the composition may be prepared as a multiple part (e.g.,2 part) composition when a crosslinker is present. In this instance thecatalyst and crosslinker are stored in separate parts, and the parts arecombined shortly before use of the composition. For example, a two partcurable composition may be prepared by combining ingredients comprisingthe alkoxy-functional polyorganosiloxane and the crosslinker to form afirst (curing agent) part by any convenient means such as mixing. Asecond (base) part may be prepared by combining starting materialscomprising a catalyst and the alkoxy-functional polyorganosiloxane byany convenient means such as mixing. The starting materials may becombined at ambient or elevated temperature and under ambient oranhydrous conditions, depending on various factors including whether aone part or multiple part composition is selected. The base part andcuring agent part may be combined by any convenient means, such asmixing, shortly before use. The base part and curing agent part may becombined in relative amounts of base: curing agent ranging from 1:1 to10:1.

The equipment used for mixing the starting materials is not specificallyrestricted. Examples of suitable mixing equipment may be selecteddepending on the type and amount of each ingredient selected. Forexample, agitated batch kettles may be used for relatively low viscositycompositions, such as compositions that would react to form gums orgels. Alternatively, continuous compounding equipment, e.g., extruderssuch as twin screw extruders, may be used for more viscous compositionsand compositions containing relatively high amounts of particulates.Exemplary methods that can be used to prepare the compositions describedherein include those disclosed in, for example, U.S. Patent PublicationsUS 2009/0291238 and US 2008/0300358.

These compositions made as described above may be stable when the storedin containers that protect the compositions from exposure to moisture,but these compositions may react via condensation reaction when exposedto atmospheric moisture.

EXAMPLES

These examples are intended to illustrate some embodiments of theinvention and should not be interpreted as limiting the scope of theinvention set forth in the claims. In the examples below, the examplesfor preparing alkoxy-functional organohydrogensiloxane oligomers wereperformed under inert conditions, i.e., the flask was purged withnitrogen before adding starting materials.

Synthesis of bis(trimethoxysilylethyl)-dimethylsiloxy-n-propylsilane(EHM)

In this Reference Example 1, crude EHM was prepared as follows:tris(dimethylsiloxy)-n-propylsilane (2.51 mol), dimethylacetoxysilane(0.502 mol), and platinum catalyst (15.8 μmol Pt) were loaded into areactor, mixed, and heated to 70° C. Vinyltrimethoxysilane (5.40 mol)was gradually added to the mixture in the reactor over 160 min tomaintain liquid temperature in the reactor of 75° C. to 90° C. Theresulting crude EHM was characterized by ¹H NMR to determine the β/αratio, acetoxy level (acetyl/propyl mole ratio), and Si—H level(Si—H/propyl mole ratio), shown in Table 1

TABLE 1 crude EHM analysis β/α ratio 89/11 acetyl/propyl mole ratio 0.19Si—H/propyl mole ratio 0.30

In this Reference Example 2, the crude EHM prepared in reference example1 was purified by distillation under 1 Torr vacuum and collected asoverhead species. The distilled EHM was characterized by ¹H NMR todetermine the β/α ratio, acetoxy level (acetyl/propyl mole ratio), andSi—H level (Si—H/propyl mole ratio), shown in Table 2, below.

TABLE 2 distilled EHM analysis β/α ratio 90/10 acetyl/propyl mole ratio0.012 Si—H/propyl mole ratio 0.31

In this Example 3, the crude EHM prepared in Reference Example 1 wastreated with activated carbon (Filtrasorb 600) in an amount of 0.3 g andH₂O (0.06 g). The mixture was stirred at 25° C. for 24 h, filtered, anddried under vacuum. The acetoxy level (acetyl/propyl mole ratio) andSi—H level (Si—H/propyl mole ratio) were measured by ¹H NMR. Aftertreatment, acetoxy level was reduced by 96% while Si—H level wasdecreased by 2%.

In this Example 4, the crude EHM prepared in Reference Example 1 wastreated with ion exchange resin as follows: Crude EHM (5 g) was mixedwith Amberlite IRA-67 (1 g). The mixture was stirred at 25° C. for 24 hand filtered. The acetoxy level (acetyl/propyl mole ratio) and Si—Hlevel (Si—H/propyl mole ratio) were measured by ¹H NMR. After treatment,acetoxy level was reduced by 98% while Si—H level was decreased by 1%.

In this Example 5, crude EHM prepared in Reference Example 1 was treatedwith aqueous ammonia as follows: Crude EHM (3 g) was mixed with ammoniasolution (28-30%, 142 μL). The mixture was stirred at 25° C. for 3 h,filtered, and dried under vacuum. The acetoxy level (acetyl/propyl moleratio) and Si—H level (Si—H/propyl mole ratio) were measured by ¹H NMR.After treatment, acetoxy level was reduced by >99% while Si—H level wasdecreased by <1%.

In this Example 6, crude EHM prepared in Reference Example 1 was treatedwith an ammonia/methanol solution as follows: Crude EHM (3 g) was mixedwith ammonia/methanol solution (7N, 0.32 mL). The mixture was stirred at25° C. for 4 h, filtered, and dried under vacuum. The acetoxy level(acetyl/propyl mole ratio) and Si—H level (Si—H/propyl mole ratio) weremeasured by ¹H NMR. After treatment, acetoxy level was reduced by >99%while Si—H level was decreased by 3%.

In this Comparative Example 7, crude EHM prepared in Reference Example 1was treated with dried ion exchange resin (no Ingredient (F)) asfollows: Crude EHM (5 g) was mixed with dried Amberlite IRA-67 (0.5 g).The mixture was stirred at 25° C. for 24 h and filtered. The acetoxylevel (acetyl/propyl mole ratio) and Si—H level (Si—H/propyl mole ratio)were measured by ¹H NMR. After treatment, acetoxy level was reduced by71% while Si—H level was decreased by 3%.

In this Comparative Example 8, crude EHM prepared in Reference Example 1was treated with CaCO₃ and H₂O as follows: Crude EHM (4 g) was mixedwith CaCO₃ (0.8 g) and H₂O (0.08 g). The mixture was stirred at 25° C.for 72 h and filtered. The acetoxy level (acetyl/propyl mole ratio) andSi—H level (Si—H/propyl mole ratio) were measured by ¹H NMR. Aftertreatment, acetoxy level was reduced by 95% while Si—H level wasdecreased by 10%.

In this Comparative Example 9, crude EHM prepared in Reference Example 1was treated with basic alumina and H₂O as follows: Crude EHM (5 g) wasmixed with basic alumina (0.5 g) and H₂O (0.1 g). The mixture wasstirred at 25° C. for 24 h, filtered, and dried under vacuum. Theacetoxy level (acetyl/propyl mole ratio) and Si—H level (Si—H/propylmole ratio) were measured by ¹H NMR. After treatment, acetoxy level wasreduced by 93% while Si—H level was decreased by 7%.

In this Comparative Example 10, crude EHM prepared in Reference Example1 was treated with sodium methoxide as follows: Crude EHM (3 g) wasmixed with NaOMe (0.15 g). The mixture was stirred at 25° C. for 48 hand filtered. The acetoxy level (acetyl/propyl mole ratio) and Si—Hlevel (Si—H/propyl mole ratio) were measured by ¹H NMR. After treatment,acetoxy level was reduced by >99% while Si—H level was decreased by 24%.

In this Comparative Example 11, crude EHM prepared in Reference Example1 was treated with water as follows: Crude EHM (5 g) was mixed with H₂O(0.06 g). The mixture was stirred at 25° C. for 24 h. The acetoxy level(acetyl/propyl mole ratio) and Si—H level (Si—H/propyl mole ratio) weremeasured by ¹H NMR. After treatment, acetoxy level was reduced by <5%while Si—H level was decreased by 91%.

TABLE 3 Summary of Treatment Results OAc/Pr Si—H/Pr Examples TypeTreatment Reduction Reduction  3 Inventive Activated carbon/H₂O   96%   2%  4 Inventive Amberlite IRA-67   98%    1%  5 InventiveNH₃/H₂O >99%  <1%  6 Inventive NH₃/MeOH >99%    3%  7 Comparative DriedAmberlite   71%    3%  8 Comparative CaCO₃/H₂O   95%   10%  9Comparative Basic alumina/H₂O   93%    7% 10 Comparative NaOMe   99%  24% 11 Comparative H₂O  <5%   91%

In this example 12, treated EHM prepared in Example 5 was purified bydistillation under 1 Torr vacuum and collected as an overhead species.The resulting distilled treated EHM was characterized by ¹H NMR todetermine the β/α ratio, acetoxy level (acetyl/propyl mole ratio), andSi—H level (Si—H/propyl mole ratio): 92/8 β/α; <0.001 Ac/Pr; 0.31Si—H/Pr.

In this Comparative Example 13, a polymethoxy-functionalpolydimethylsiloxane was prepared as follows: To a Max 300 LongSpeedmixer cup was added 450.00 g SILASTIC™ SFD-128(bis-vinyldimethylsiloxy terminated polydimethylsiloxane with DP=800 to1,000) available from Dow Silicones Corporation of Midland, Mich., USAand 7.28 g (80% conversion) of EHM prepared in Reference Example 2. Theresulting mixture was blended on a 600.2 Vac-P Flaktek Speedmixer for 30sec at 2000 rpm. Next, 1.73 g (2 ppm) 3-0313 INT Pt catalyst was addedto the cup and mixed for 90 sec at 2000 rpm. The resultingpolymethoxy-functional polydimethylsiloxane polymer was allowed to restat room temperature to complete the capping reaction and was analyzedthe next day. Viscosity was measured on an ARES constant strainrheometer using a 25 mm parallel cone and plate, and a steady rate sweepfrom 0.1-10 (s⁻¹). Viscosity Results are shown below in Table 4.

In this Example 14, to a Max 300 Long Speedmixer cup was added 450.00 gSILASTIC™ SFD-128 and 7.31 g (80% conversion) of distilled, treated EHMfrom Example 12. The resulting mixture was blended on a 600.2 Vac-PFlaktek Speedmixer for 30 sec at 2000 rpm. Next, 1.73 g (3 ppm)Karstedt's catalyst diluted with DOWSIL™ SFD-120, was added to the cup,and mixed for 90 sec at 2000 rpm. The resulting polymethoxy-functionalpolydimethylsiloxane polymer was allowed to rest at room temperature tocomplete the capping reaction and was analyzed the next day. Viscositywas measured on an ARES constant strain rheometer using a 25 mm parallelcone and plate, and a steady rate sweep from 0.1-10 (s⁻¹). ViscosityResults are shown below in Table 4.

TABLE 4 Initial 3 weeks 50° C. viscosity viscosity (cP) (cP) Comparative69,700 169,800 Example 13 Example 14 75,100 83,800

Comparative Example 13 and Example 14 showed that thepolymethoxy-functional polydimethylsiloxane treated according to themethod described herein had better stability (show by less viscosityincrease after 3 week aging at 50° C.).

INDUSTRIAL APPLICABILITY

The examples above showed that the method described herein is capable ofproducing an alkoxy-functional organohydrogensiloxane oligomer with goodyield and selectivity and with minimized processing time and steps.Furthermore, example 14 and comparative example 13 above showed thatwhen a polyorganosiloxane was endblocked with an alkoxy-functionalorganohydrogensiloxane oligomer prepared by the method described herein,the resulting endblocked polyorganosiloxane had better stability asshown by small viscosity increase as compared to a comparativepolymethoxy-functional polydimethylsiloxane prepared without using step2) of the method described herein.

INDUSTRIAL APPLICABILITY

Without wishing to be bound by theory, it is thought that one of thebenefits of the method described herein is minimizing number of processsteps and energy required for preparing the product comprising thealkoxy-functional organohydrogensiloxane oligomer. Therefore, theoptional distillation step after step 1) and before step 2) may beeliminated.

DEFINITIONS AND USAGE OF TERMS

Unless otherwise indicated by the context of the specification: allamounts, ratios, and percentages herein are by weight; the articles ‘a’,‘an’, and ‘the’ each refer to one or more; and the singular includes theplural. The SUMMARY and ABSTRACT are hereby incorporated by reference.The terms “comprising” or “comprise” are used herein in their broadestsense to mean and encompass the notions of “including,” “include,”“consist(ing) essentially of,” and “consist(ing) of. The use of “forexample,” “e.g.,” “such as,” and “including” to list illustrativeexamples does not limit to only the listed examples. Thus, “for example”or “such as” means “for example, but not limited to” or “such as, butnot limited to” and encompasses other similar or equivalent examples.

“Yield” means molar amount alkoxy-functional organohydrogensiloxaneoligomer produced/molar amount alkoxy-functional organohydrogensiloxaneoligomer possible based on the amount of limiting reagent (thealiphatically unsaturated alkoxysilane). “Selectivity” means the ratioof linear isomer/branched isomer of the alkoxy-functionalorganohydrogensiloxane (where isomers have the same molecular weight).

The abbreviations used herein have the definitions in Table 4.

TABLE 4 Abbreviations Abbreviation Definition DMAS dimethylacetoxysilaneEHM bis(trimethoxysilylethyl)-dimethylsiloxy-n-propylsilane h hours mmmillimeters N Normal NMR Nuclear Magnetic Resonance (provide a testmethod for the 1HNMR used in the examples) OAc acetoxy PDMSpolydimethylsiloxane rpm revolutions per minute Pr propyl Pr-Ttris(dimethylsiloxy)-n-propylsilane Pr-T EHMPrSi(OSiMe₂CH₂CH₂Si(OMe)₃)₂(OSiMe₂H) including others isomers rpmrevolutions per minute RT room temperature of 25° C. +/− 5° C. secseconds μL microliters Vi vinyl VTM Vinyltrimethoxysilane, example ofstarting material B)

1. A method for preparing a product comprising an alkoxy-functionalorganohydrogensiloxane oligomer, where the method comprises: 1) reactingstarting materials comprising: (A) a polyorganohydrogensiloxane oligomerof unit formula: (HR¹ ₂SiO_(1/2))_(e)(R¹₃SiO_(1/2))f(HR¹SiO_(2/2))_(g)(R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(j)(SiO_(4/2))_(k) wheresubscripts e, f, g, h, i, j, and k have values such that 5≥e≥0, 5≥f≥0,10≥g≥0, 5≥h≥0, subscript i is 0 or 1, 5≥j≥0, subscript k is 0 or 1, withthe proviso that a quantity (e+g+j) >2, and a quantity(e+f+g+h+i+j+k)≤50; and each R¹ is independently selected from the groupconsisting of a monovalent hydrocarbon group of 1 to 18 carbon and amonovalent halogenated hydrocarbon group of 1 to 18 carbon atoms; and(B) an aliphatically unsaturated alkoxysilane of formula:

 where R¹ is as described above, R² is an aliphatically unsaturatedmonovalent hydrocarbon group of 2 to 18 carbon atoms, each R³ isindependently a monovalent hydrocarbon group of 1 to 18 carbon atoms,and subscript c is 0 or 1; in the presence of (C) a platinum group metalcatalyst; and (D) a hydro(acyloxy)-functional silicon compound offormula:

 where each R⁵ is independently a monovalent hydrocarbon group of 1 to18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18carbon atoms, and R⁶ is a monovalent hydrocarbon group of 1 to 18 carbonatoms, thereby preparing a reaction product comprising thealkoxy-functional organohydrogensiloxane oligomer; and thereafter 2)treating the reaction product prepared in step 1) with a treating agentcomprising (E) a sorbent selected from the group consisting of (E-1) anactivated carbon, (E-2) an ion exchange resin, (E-3) a compound offormula NR⁸ _(x)R⁹ _(y)R¹⁰ _((3-x-y)), where R⁸, R⁹, and R¹⁰ are eachindependently selected from the group consisting of a hydrogen atom anda monovalent hydrocarbon group of 1 to 18 carbon atoms, subscript x is 0to 3, subscript y is 0 to 3, and a quantity (x+y)≤3; (E-4) a compound offormula

 where R¹¹ is selected from the group consisting of a hydrogen atom anda monovalent hydrocarbon group of 1 to 18 carbon atoms, and R¹² is adivalent hydrocarbon group of 1 to 18 carbon atoms; and (E-5) acombination of two or more of (E-1) to (E-4); and (F) a compound offormula HOR⁷, where R⁷ is a hydrogen atom or a monovalent hydrocarbongroup of 1 to 18 carbon atoms, thereby preparing the product comprisingthe alkoxy-functional organohydrogensiloxane oligomer; and 3) distillingthe product of step 2), thereby recovering the alkoxy-functionalorganohydrogensiloxane oligomer.
 2. The method of claim 1, where (E) thetreating agent comprises ammonia (NH₃).
 3. The method of claim 1, where(F) the compound of formula HOR⁴ is water or methanol.
 4. The method ofclaim 1, where the alkoxy-functional organohydrogensiloxane oligomer hasunit formula:

(HR¹ ₂SiO_(1/2))_(n)(R¹ ₃SiO_(1/2))_(f)(HR¹SiO_(2/2))_(o) (R¹₂SiO_(2/2))_(h)(R¹SiO_(3/2))_(i)(HSiO_(3/2))_(p)(SiO_(4/2))_(k), whereR¹, R³, and subscripts c, f, h, i, and k are as described above,subscript b is 0 to 2, m>0, and a quantity (m+n+o+p)=(e+g+j), and each Dis independently a divalent hydrocarbon group of 2 to 18 carbon atoms,with the proviso that >90 mol % of all D groups produced in step 1) arelinear.
 5. The method of claim 1, where (A) thepolyorganohydrogensiloxane oligomer has formula:

where subscript a is 0 to
 10. 6. The method of claim 5, where thealkoxy-functional organohydrogensiloxane oligomer has formula:

where D is a divalent hydrocarbon group of 2 to 18 carbon atoms.
 7. Themethod of claim 1, where (A) the polyorganohydrogensiloxane oligomer hasunit formula: (HR¹ ₂SiO_(1/2))₃(R¹ ₂SiO_(2/2))_(q)(R¹SiO_(3/2)), wheresubscript q is 0 to
 3. 8. The method of claim 7, where (A) thepolyorganohydrogensiloxane oligomer has formula:


9. The method of claim 8, where alkoxy-functional organohydrogensiloxaneoligomer has formulae comprising:

where each D is independently a divalent hydrocarbon group of 2 to 18carbon atoms, with the proviso that >90 mol % of D are linear divalenthydrocarbon groups.
 10. The method of claim 1, where theorganohydrogensiloxane oligomer is a cyclic organohydrogensiloxaneoligomer of unit formula: (R¹ ₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(s), wheresubscript s≥3, and subscript v≥0.
 11. The method of claim 10, where thealkoxy-functional organohydrogensiloxane oligomer has unit formula: (R¹₂SiO_(2/2))_(v)(R¹HSiO_(2/2))_(t)

where subscript t≥0, subscript u≥1, and a quantity (t+u)=s.
 12. Themethod of claim 1, where step 2) is performed directly after step 1)without a purification step after step 1) and before step 2).
 13. Amethod for preparing a polyalkoxy-functional polyorganosiloxane, wherethe method comprises: (1) reacting starting materials comprising: (a)the alkoxy-functional organohydrogensiloxane oligomer of claim 1; (b) apolyorganosiloxane having, per molecule, an average of at least twoaliphatically unsaturated monovalent hydrocarbon groups; and (c) ahydrosilylation reaction catalyst.
 14. The method of claim 12, wherestarting material (b) is a polydiorganosiloxane of formula:

where subscript n is 1 to 2,000.
 15. The method of claim 13, where thepolyalkoxy-functional polyorganosiloxane has formula:

where each D¹ is independently a divalent hydrocarbon group.